Instantaneous impedance measurements on aluminium using a Schroeder multisine excitation signal

Abstract Time-varying phenomena, such as crystallographic pitting corrosion, can be investigated by electrochemical impedance spectroscopy (EIS). For this purpose, a stepped sine excitation is most frequently used. However, when the frequency ranges from 25 Hz down to 15 mHz this experiment takes at least 30 min. In this work a periodic Schroeder multisine excitation signal is presented, by which the measurement time can be reduced to 2 min for the same frequency range. To evaluate the correctness of the EIS results obtained with the multisine, data was acquired for aluminum (99.5 wt.%) immersed in 0.5 M NaCl with oxygen bubbling by means of a stepped sine, next a multsine and finally a stepped sine excitation. From the spectra obtained with both stepped sines a new virtual spectrum is calculated as if all excited frequencies would have been recorded at the moment when the multisine was imposed to the system. A comparison of the multisine spectrum with this interpolated spectrum was then used for validation. The results show that the instantaneous behaviour of a time-varying system, observed during EIS is better approximated by the use of a multisine excitation signal. Moreover, the approximation further ameliorates when the immersion time evolves.

[1]  Mark E. Orazem,et al.  Measurement Models for Electrochemical Impedance Spectroscopy I . Demonstration of Applicability , 1992 .

[2]  J. Vereecken,et al.  Influence of different anions on the behaviour of aluminium in aqueous solutions , 2002 .

[3]  Yongku Kang,et al.  The protectivity of aluminum and its alloys with transition metals , 1997 .

[4]  Claude Gabrielli,et al.  Comparison of sine wave and white noise analysis for electrochemical impedance measurements , 1992 .

[5]  C. Mayer,et al.  AC-Impedance measurements on aluminium in chloride containing solutions and below the pitting potential , 1990 .

[6]  F. Mansfeld,et al.  Evaluation of Anodized Aluminum Surfaces with Electrochemical Impedance Spectroscopy , 1988 .

[7]  M. Richardson,et al.  Monitoring the corrosion behaviour of chromate-passivated aluminium alloy 2014 A-T6 by electrochemical impedance spectroscopy during salt fog exposure , 1999 .

[8]  M. Thubrikar,et al.  On the Kinetics of the Breakdown of Passivity of Preanodized Aluminum by Chloride Ions , 1975 .

[9]  J. Chavarín,et al.  Electrochemical Investigations of the Activation Mechanism of Aluminum , 1991 .

[10]  Manfred R. Schroeder,et al.  Synthesis of low-peak-factor signals and binary sequences with low autocorrelation (Corresp.) , 1970, IEEE Trans. Inf. Theory.

[11]  S. Pyun,et al.  Effects of sulphate ion additives on the pitting corrosion of pure aluminium in 0.01 M NaCl solution , 2000 .

[12]  F. Mansfeld,et al.  Pitting and Passivation of Al Alloys and Al‐Based Metal Matrix Composites , 1990 .

[13]  Mark E. Orazem,et al.  Application of Measurement Models to Impedance Spectroscopy III . Evaluation of Consistency with the Kramers‐Kronig Relations , 1995 .

[14]  Kazimierz Darowicki,et al.  Theoretical description of the measuring method of instantaneous impedance spectra , 2000 .

[15]  L. García-Rubio,et al.  Application of Measurement Models to Impedance Spectroscopy II . Determination of the Stochastic Contribution to the Error Structure , 1995 .

[16]  Florian Mansfeld,et al.  Electrochemical impedance spectroscopy (EIS) as a new tool for investigating methods of corrosion protection , 1990 .

[17]  Z. Szklarska‐Śmiałowska Pitting corrosion of aluminum , 1999 .

[18]  F. Mansfeld,et al.  Impedance spectra for aluminum 7075 during the early stages of immersion in sodium chloride , 1993 .

[19]  Nadine Pébère,et al.  An investigation of the corrosion inhibition of pure aluminum in neutral and acidic chloride solutions , 1996 .

[20]  F. Bellucci,et al.  Degradation behaviour of 6013-T6, 2024-T3 alloys and pure aluminium in different aqueous media , 1997 .

[21]  S. Pyun,et al.  Effects of Sulfate and Nitrate Ion Additives on Pit Growth of Pure Aluminum in 0.1 M Sodium Chloride Solution , 2000 .

[22]  K. Darowicki,et al.  Instantaneous impedance spectra of a non-stationary model electrical system , 2000 .

[23]  R. Alkire,et al.  Microelectrochemical Studies of Pit Initiation at Single Inclusions in Al 2024-T3 , 2001 .

[24]  R. N. Schindler,et al.  A new approach to the problem of good and bad impedance data in electrochemical impedance spectroscopy , 1994 .

[25]  R. N. Schindler,et al.  Validation of experimental data in electrochemical impedance spectroscopy , 1993 .

[26]  K. Jüttner Electrochemical impedance spectroscopy (EIS) of corrosion processes on inhomogeneous surfaces , 1990 .

[27]  K. Nisancioglu,et al.  Significance of Thermomechanical Processing in Determining Corrosion Behavior and Surface Quality of Aluminum Alloys , 2000 .

[28]  Yves Rolain,et al.  Broadband versus stepped sine FRF measurements , 2000, IEEE Trans. Instrum. Meas..

[29]  Robert P. Wei,et al.  In-Situ Monitoring of Pitting Corrosion in Aluminum Alloy 2024 , 1998 .

[30]  T. H. Nguyen,et al.  On the Mechanism of Pitting of Aluminum , 1979 .

[31]  R. N. Schindler,et al.  Effect of sample nonlinearity on the performance of time domain electrochemical impedance spectroscopy , 1995 .

[32]  A. Wiȩckowski,et al.  Adsorption of sulfate and chloride ions on aluminum , 1998 .